Synthesis, characterisation, reactivity and stereochemical studies of heterobimetallic complexes containing an orthometallated cyclopentadienylphosphine bridge
| Autor: | Claude Moïse, Sandrine Rigny, J.C. Leblanc, Bernd Nuber |
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| Rok vydání: | 1997 |
| Předmět: | |
| Zdroj: | Journal of the Chemical Society, Dalton Transactions. :1187-1194 |
| ISSN: | 1364-5447 0300-9246 |
| DOI: | 10.1039/a607223b |
| Popis: | The heterobimetallic diastereoisomer complexes [X(η 5 -C 5 H 5 )Mo{(η 5 -C 5 H 4 )PPh(o-C 6 H 4 )}M(CO) 5 ] (X = Cl 1 and 1′ or I 2 and 2′; M = Cr a, Mo b or W c) containing an orthometallated cyclopentadienylphosphine bridge have been prepared and characterised. They were obtained by reaction of Li[M(CO) 5 (PPh 2 )] and the corresponding metallocene dichloride in tetrahydrofuran. The crystal structures of 1a and 2c showed that the η 5 -C 5 H 4 PPh[M(CO) 5 ]C 6 H 4 fragment chelates the Mo. Similarly, methylated complexes 3 were prepared when [Mo(η 5 -C 5 H 4 Me) 2 Cl 2 ] was used as metallocene dichloride; the 1,3 regioselectivity of these reactions has been assigned on the basis of 1 H and 31 P NMR data. Compound 1c reacted with LiAlH 4 to give a dihydride molybdenocene complex [H(η 5 -C 5 H 5 )Mo(η 5 -C 5 H 4 PPh 2 )HW(CO) 4 ]. Alkylated diastereoisomers [R(η 5 -C 5 H 5 )Mo{(η 5 -C 5 H 4 )PPh(o-C 6 H 4 )}M(CO) 5 ] (R = Me or Et) were obtained by reaction of 1c with a Grignard reagent; cleavage of the Mo–Me bond with hydrochloric acid has been found to occur with retention of configuration. |
| Databáze: | OpenAIRE |
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